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TNG HP THY NHIT V NGHIN CU TNH CHT

CA CC HT VI CU V NANO HNH CU XP ZnS
Nguyn Tr Tun1, Nguyn Vn t2, Nguyn Th Phng Em3 v L Vn Nhn4

ABSTRACT
ZnS nanoparticles were hydrothermally synthesized at 200 C for 4 and 7 hours using
sodium thiosulfate (Na2S2O3) and zinc chloride as initial materials. Scanning electron
microscopy (SEM) images showed the co-existance of individual ZnS nanoparticles and
microspheres formed by the nanoparticles. When acrylamide was added to the
hydrothermal synthesis process as a surfactant, ZnS porous nanospheres were obtained.
X-ray diffraction (XRD) revealed that the average size of ZnS nanocrystallites, estimated
by the Debye-Sherrer formula, was about 4 nm. Photoluminescence excited (PLE) spectra
of the material exhibited two blue shifts (~ 64 nm and ~ 24 nm) compared with the
Photoluminescence (PL) peak of bulk ZnS. It is known to arise due to quantum
confinement effect.
Keywords: Nanoparticles; porous nanospheres; microspheres; hydrothermally
synthesis
Title: Hydrothermal synthesis and study on properties of ZnS micropheres and porous
nanospheres

TM TT
Cc ht nano tinh th ZnS c tng hp thy nhit 200 oC trong 4 gi v 7 gi, bng
cch s dng cht Na2S2O3 (sodium thiosulfate) and ZnCl2 lm vt liu ban u. nh hin
vi in t qut cho thy s tn ti ng thi cc ht nano ZnS ring r v cc ht vi hnh
cu c to thnh bi cc ht nano. Khi cht acrylamide (cht hot ng b mt) c
cho thm vo trong qu trnh tng hp thy nhit, cc nano hnh cu xp ZnS c to
thnh. S dng phng php nhiu x tia X (XRD) o kch thc trung bnh ca nano
tinh th ZnS bng cng thc Debye-Sherrer, c gi tr khong 4 nm. Ph kch thch hunh
quang (PLE: photoluminescence-excitation) ca vt liu cho thy rng c 2 dch chuyn
rt mnh (~64 v 24 nm) v pha bc sng ngn (blue shift) so vi nh hunh quang
(PL:Photoluminescence) ca ZnS khi. S dch chuyn ny do nh hng ca hiu ng
giam gi lng t.
T kha: ht nano, nano hnh cu xp, vi hnh cu, tng hp thy nhit

1 GII THIU
ZnS l mt bn dn II-VI quan trng, c nng lng vng cm ln, khong 3.7 eV
300 K, n c s dng lm vt liu hunh quang cho ng tia cathode [1], bt
phosphor cho mn hnh phng v trong linh kin in hunh quang mng mng
[2]. Gn y, nhiu nhm nghin cu quan tm n vt liu nano c hnh dng c
bit v cc tnh cht mi c mong i ca n. Vt liu nano ZnS mt chiu
c ch to nh l que nano [3], dy nano [4-7], ai nano [8], ng nano [9], hnh
1

B mn Vt l, Khoa Khoa hc t nhin, Trng i hc Cn Th

B mn Ha hc, Khoa Khoa hc, Trng i hc Cn Th
3
Khoa c bn, Trng i hc Tin Giang
4
B mn Vt l S phm, Khoa S phm, Trng i hc Cn Th
2

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cu nano [10-12]. Hnh cu nano xp c th ng dng dng lm vt liu nh l

tinh th quang t, b lc, xc tc,... V cc kh nng ng dng ca vt liu ny,
nn chng ti ch to ht nano hnh cu xp ZnS bng phng php thy nhit
200 C trong 4 gi v 7 gi, khi cht acrylamide (cht hot ng b mt) cho
thm vo trong qu trnh phn ng.
2 THC NGHIM
2.1 Tng hp nano tinh th ZnS
Trong th nghim ny, 4.08 g ZnCl2 khan v 7.44 g Na2S2O3.5H2O c vo
Teflon ca bnh thy nhit c th tch 150 ml cng vi nc kh ion, chim tng
cng th tch 120 ml (80%) ca Teflon. Bnh thy nhit c ng kn nhit
200 oC trong 4 v 7 gi. Sau khi thi gian phn ng ht, kt qu thu c l
cht lng trng c. Dung dch ny c em quay ly tm, lc ra 2 ln bng nc
kh ion v cn tuyt i, sau em sy kh trong chn khng (10-2 10-3 Torr)
nhit 70 oC trong 15 gi. Kt qu, sn phm thu c l bt nano tinh th ZnS.
2.2 Tng hp nano hnh cu xp ZnS
Tng hp nano hnh cu xp ZnS, 3.6 g acrylamide s dng nh cht hot ng b
mt, c thm vo th nghim trn, nhit 200 oC trong 4 gi. Phng php
tng hp ny tng t nh phng php ca Changlong Jiang v cng s [10].
2.3 Cc phng php kho st thc nghim
Cc mu thu c sau khi tng hp c kho st tnh cht cu trc bng gin
nhiu x tia X (D8 Advance Bruker- c) ti Khoa Ha hc, Trng i hc
Khoa hc T nhin, i hc Quc gia H Ni. Kch thc v hnh thi cu trc
ca mu c kho st bng nh hin vi in t qut (FESEM) v nh hin vi
truyn qua (TEM) ti Vin v sinh Dch t trung ng. Tnh cht quang ca vt
liu c o bng my o ph hunh quang FL3-22 (Jobin Yvon-Spex, M) ti
Trung tm Khoa hc Vt liu- HKH T nhin H Ni.
3 KT QU
3.1 Tnh cht cu trc
Hnh 1 l gin nhiu x tia X ca ca mu nano tinh th ZnS nhn c sau qu
trnh tng hp bng phng php thy nhit, 200 oC trong 4 gi (4 h), 7 gi (7 h)
v 4 gi (4 h(a)) c cht hot ng b mt acrylamide (a).

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Hnh 1: Gin nhiu x tia X ca mu nano tinh th ZnS tng hp thy nhit
200 oC trong 7h, 4 gi v 4 gi c cht hot ng b mt acrylamide

C th thy trong hnh 1, gin nhiu x tia X c c trng bi 3 nh nhiu

x c cng yu v rng bn ph ln. V tr cc nh ny l hon ton tng
ng vi nhiu x trn 3 mt (111), (220) v (311) ca ZnS c cu trc lp phng
gi km. Kt qu ny khng nh bt nhn c t quy trnh tng hp ca chng
ti l ZnS. Cng yu v rng bn ph ln ca cc nh nhiu x cho thy
cc tinh th nhn c c kch thc nh v kt tinh thp. Da vo gin
nhiu x tia X v cng thc Debye-Sherrer, chng ti tnh c kch thc tinh th
ca nano ZnS ca mu 1, 2 v 3 c biu din bng 1. Da vo bng 1, chng
ti thy kch thc tinh th ca nano ZnS ca mu 1 v 2 l thay i khng nhiu.
i vi mu 3, kch thc tinh th ca nano ZnS l ~3 nm, nh hn so vi hai
mu trn.
Bng 1: Kch thc trung bnh ca ht nano tinh th ZnS c tng hp thy nhit
200 oC trong 4 gi, 7 gi v 4 gi c cht hot ng b mt acrylamide

Mu
Thi gian thy nhit
Kch thc tinh th

1
4 gi
~9 nm

2
7 gi
~12 nm

3
4 gi (a)
~3 nm

nh FESEM ca mu 1 v 2 c biu din hnh 2. Hnh 2a l nh FESEM mu

1, cho thy nh ca mt ht vi cu c ng knh khong 1m, b mt ca ht vi
cu ny nhm, khng c nhn. Hnh 2b l nh FESEM ht vi cu c phng
to ln hai ln, cho thy cc ht nano b mt ca ht vi cu c kch thc khong
15 nm, ln hn kch thc c tnh ton da trn gin nhiu x tia X.
a
b
c
d

Hnh 2: nh FESEM ca ht nano tinh th ZnS c tng hp thy nhit

nhit 200 oC trong 4 gi v 7h

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iu ny chng t cc ht tinh th nano ZnS to thnh cc ht vi cu ZnS. Hnh 2c

l nh FESEM mu 2, cho thy ngoi cc ht vi cu ZnS c ng knh khong 15 m, cn c ln cc ht nano c kch thc trung bnh khong 20 nm c biu
din hnh 2d. Nh vy, khi tng hp thy nhit mu 2 (200 oC, 7 gi), c thi
gian ln hn mu 1 (200 oC, 4 gi), th kch thc trung bnh ca cc ht nano tinh
th ZnS ln hn v kch thc khong 5 nm, iu chng t cc ht b kt m
khi thi gian tng hp thy nhit lu hn 4 gi.
nh FESEM ca mu 3 c biu din hnh 3. Hnh 3a cho thy nh cc ht
nano ZnS c dng hnh cu xp, ng knh ca cc ht nano hnh cu xp c kch
thc khong 130-230 nm. Nguyn nhn to ra ht nano hnh cu xp, c th l do
cc bt kh SO2 to ra trong qu trnh phn ng, bay ln lm cho cc ht nano hnh
cu c nhng l nh to nn hnh cu xp. Hnh 3b cho thy cc ht nano ZnS c
kch thc khong 10 nm cu thnh cc ht nano hnh cu xp, khi tng hp thy
nhit mu 3 do c cht xc tc b mt acrylamide thm vo trong mu, ngn khng
cho ht kt t ln ln c.
a

Hnh 3: nh FESEM ca ht nano tinh th ZnS c tng hp thy nhit nhit

200 oC trong 4 gi c cht hot ng b mt acrylamide

xc nh kch thc v hnh thi hc ca ht chnh xc hn, chng ti chp nh

TEM ca mu. Hnh 4 l nh TEM ca cc ht nano c thy nhit 200 oC
khng c cht acrylamide, cc ht ny c kch thc ~10 nm v kt m li vi
nhau. Kch thc ht ny kh ph hp vi kch thc tnh bng gin tia X.

Hnh 4: nh TEM ca ht nano tinh th ZnS c tng hp thy nhit nhit 200 oC
trong 4 gi, khng c acrylamide
4

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Hnh 5 l nh TEM ca ht nano tinh th ZnS c tng hp thy nhit nhit

200oC trong 4 gi, c cht hot ng b mt acrylamide.

b
80 nm

60 nm

30 nm

Hnh 5: nh TEM ca ht nano tinh th ZnS c tng hp thy nhit nhit 200 oC 4 gi, c cht hot ng b mt acrylamide

Da vo hnh 5a, cho thy cc ht nano ny c kch thc kh nh ~2-3 nm, do

cht hot ng b mt bm vo b mt ca cc ht nano khng cho cc ht kt
t li vi nhau. Hnh 5b, cho thy cc ht nano cu thnh cc nano hnh cu xp
ZnS, c kch thc trung bnh ~30-80 nm. Kch thc ca cc ht nano Zns ny
tng i ph hp vi kch thc tnh bng gin nhiu x tia X v nh FESEM.
3.2 Tnh cht hunh quang
Hnh 6, l ph kch thch hunh quang ca ht nano v ht nano hnh cu xp ZnS
c tng hp thy nhit 200 oC trong 4 gi v 7 gi khng c cht acrylamide
v 4 gi c cht acrylamide. Vng ph PLE rng t 250-350 nm, hai nh chnh
nhn c bao gm hai vng ph c trng vi cc i tng ng ~280 v ~320
nm, so vi ph kch thch hunh quang ca ZnS khi 344 nm [13], c s dch
chuyn v pha bc sng ngn, c nng lng cao (blue shift) rt mnh ~64 nm
v 24 nm tng ng. Hin tng dch chuyn ny lin quan n hin hiu ng
giam gi lng t mnh, khi kch thc ht gim xung 2-3 nm. T hnh 6, ph
hunh quang ca cc mu ZnS khng c v c cht hot ng b acrylamide c
tng hp thy nhit, chng ti quan st thy vng pht x rng ~400-500 nm, c
nh hunh quang cc i 436 nm. nh pht x ny thng l do cc sai hng
v trng thi b mt ca nano ZnS gy nn.

Hnh 6: Ph PLE v PL ca nano tinh th ZnS c tng hp thy nhit, vi em: 440 nm
v ex: 280 nm
5

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Theo cc cng b gn y, nh hunh quang mu xanh dng (blue) thng c

quan st thy cc mu nano tinh th ZnS vi di ph khong 430-464 nm [6,14].
y c xem nh l nh pht x lin quan n sai hng ca ZnS. Mt s cng
trnh gii thch nguyn nhn ca pht x xanh dng ca ZnS l do cc nt khuyt
S [15].
4 KT LUN
Trong bi bo ny, chng ti trnh by qui trnh thy nhit ch to cc ht
nano v vi cu ZnS 200 oC trong 4 gi v 7 gi. ng thi trnh by k thut ch
to ht nano hnh cu xp ZnS 200 oC trong 4 gi khi thm vo cht hot ng
b mt acrylamide, nano hnh cu xp ZnS c hnh thnh khi c bong bng kh
SO2 trong sut qu trnh phn ng. Tnh cht quang ca nano hnh cu xp ZnS
c nghin cu bng ph PLE v PL. nh ph kch thch hunh quang dch
chuyn v pha bc sng ngn (blue shift) rt mnh ~64 v 24 nm so vi nh ca
ZnS khi. Phng php ny ang c p dng ch to cc ht nano hnh cu
xp v c khc.
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